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14-Electron Four-Coordinate Ru(II) Carbyl Complexes and their Five-Coordinate Precursors : Synthesis, Double Agostic Interactions, and Reactivity

14-Electron Four-Coordinate Ru(II) Carbyl Complexes and their Five-Coordinate Precursors : Synthesis, Double Agostic Interactions, and Reactivity

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WINTER, Rainer, Dejian HUANG, William E. STREIB, John C. BOLLINGER, Kenneth G. CAULTON, Thomas SCHEIRING, 1999. 14-Electron Four-Coordinate Ru(II) Carbyl Complexes and their Five-Coordinate Precursors : Synthesis, Double Agostic Interactions, and Reactivity. In: Journal of the American Chemical Society. 121(35), pp. 8087-8097. ISSN 0002-7863

@article{Winter199914-El-13933, title={14-Electron Four-Coordinate Ru(II) Carbyl Complexes and their Five-Coordinate Precursors : Synthesis, Double Agostic Interactions, and Reactivity}, year={1999}, doi={10.1021/ja990621w}, number={35}, volume={121}, issn={0002-7863}, journal={Journal of the American Chemical Society}, pages={8087--8097}, author={Winter, Rainer and Huang, Dejian and Streib, William E. and Bollinger, John C. and Caulton, Kenneth G. and Scheiring, Thomas}, note={Publikation aus Zusammenarbeitsprojekten} }

<rdf:RDF xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:dcterms="http://purl.org/dc/terms/" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/13933"> <dc:creator>Huang, Dejian</dc:creator> <dc:creator>Scheiring, Thomas</dc:creator> <dcterms:rights rdf:resource="http://nbn-resolving.org/urn:nbn:de:bsz:352-20140905103605204-4002607-1"/> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-07-04T08:01:46Z</dc:date> <dc:contributor>Scheiring, Thomas</dc:contributor> <dc:creator>Bollinger, John C.</dc:creator> <dcterms:issued>1999</dcterms:issued> <dc:language>eng</dc:language> <dcterms:bibliographicCitation>First publ. in: Journal of the American Chemical Society 121(1999), 35, pp. 8087–8097</dcterms:bibliographicCitation> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-07-04T08:01:46Z</dcterms:available> <dc:contributor>Winter, Rainer</dc:contributor> <dcterms:title>14-Electron Four-Coordinate Ru(II) Carbyl Complexes and their Five-Coordinate Precursors : Synthesis, Double Agostic Interactions, and Reactivity</dcterms:title> <dc:contributor>Huang, Dejian</dc:contributor> <dc:contributor>Streib, William E.</dc:contributor> <dc:rights>deposit-license</dc:rights> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/13933"/> <dc:contributor>Caulton, Kenneth G.</dc:contributor> <dc:creator>Caulton, Kenneth G.</dc:creator> <dc:creator>Winter, Rainer</dc:creator> <dc:creator>Streib, William E.</dc:creator> <dcterms:abstract xml:lang="eng">The structure of five-coordinate Ru(II) complexes RuHCl(CO)(PiPr3)2, 1, RuCl2(CO)(PiPr3)2, 2, and Ru(Ph)Cl(CO)(PtBu2Me)2, 12, are reported. All three of these complexes have square-based pyramid geometry with the strongest σ-donor ligand trans to the vacant site. These 16-electron complexes do not show bona fide agostic interactions. This is attributed to the strong trans influence ligand (H, CO, and Ph) and π-donation of the Cl, which is further supported by the fact that two agostic interactions are present in the Cl- removal product of 12, i.e., the four-coordinate [RuPh(CO)L2]BAr‘4 (L = PtBu2Me, Ar‘ = 3,5-C6H3(CF3)2), 16. Structural comparison of 16 and 12 reveals that removal of Cl- does not change the remaining ligand arrangements but creates two low-lying LUMOs for agostic interactions, which persist in solution as evidenced by IR spectroscopy. Reactions of 16 with E−H (E = B, C(sp)) bonds cleave the Ru−Ph bond and form Ru−E/H bonds by different mechanisms. The reaction with catecholborane gives [RuH(CO)L2]BAr‘4, which further reacts with catecholborane to give [Ru(BR2)(CO)L2]BAr‘4. However, the reaction with Me3SiCCH undergoes a multistep transformation to give a PhCCSiMe3- and Me3SiCCH-coupled product, the mechanism of which is discussed. Reaction of RuCl2(CO)L2 with 1 equiv MeLi affords RuMeCl(CO)L2, 5, which further reacts with MeLi forming RuMe2(CO)L2, 7. Variable-temperature 13C{1H} NMR spectra reveal the two methyls in 7 are inequivalent and exchange by overcoming an energy barrier of 6.8 kcal/mol at −30 °C. The chloride of 5 can be removed to give [RuMe(CO)L2]BAr‘4.</dcterms:abstract> <dc:contributor>Bollinger, John C.</dc:contributor> </rdf:Description> </rdf:RDF>

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